I can think of worse things to get a mate to do without training, but not many.
If you told me your mate ran a marathon last week, this answer would not change. It is not about how fit they are, it is about how bike fit they are.
Years ago (when I was mid in my 20's) I was driving home for work on a Friday afternoon. The radio advertised a 40/100km fun ride happening locally, sponsored by my LBS that was just a block ahead of me. I stopped, walked in to sign up for the 40, decided what the... and signed up for the 100. I had been off my bike for over 8 months, initially due injury, then got into running and the bike collected dust. Before that I had complete a few 100 milers on that bike. I had a good bike fit and was fit, but was not bike fit.
I did the 100km, in a respectable time considering, but it hurt. It hurt a lot more the next day, no way was I riding far (I did a very easy 10km to get things moving). You will likely have issues with saddle comfort, if the road bike is a racer, your friend may struggle with the length of time in the position needed. Given your mate is on a borrowed bike and not an experienced cyclist, the bike fit is likely to be poor.
What I would do is plan on a much lower milage for the first few days, building up over a couple of weeks. Allow for plenty of time off bike including full rest days and short days. Your first two weeks will need to have conservative, or very flexible, plans.
Most likely the biggest problem will be saddle soreness and chaffing. With no pre-conditioning, on a borrowed bike, 100km (4 hours in the saddle at 25km/h average) is likely to make things rather uncomfortable. If doing this every day, no time to recover.
Your friend really needs to get a bike (ideally the one they are borrowing) and make the time to put in a couple of back-to-back 80km+ rides. Ideally you join them and work out how you ride together (I expect you, as the stronger and more experienced rider, will take point much of the time). From the information gained, you can then work out a plan that has a greater chance of a successful trip. If your friend cannot put aside time for a couple of rides, you will need to assess your friend's tolerance for discomfort, and consider if it is a trip for another time.